CN113477258B - Carbonyl sulfide removal catalyst for blast furnace top gas and preparation method thereof - Google Patents
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Abstract
The invention relates toThe field of strong steel manufacturing, and discloses a carbonyl sulfide removal catalyst for blast furnace top gas, which is prepared from the following raw materials in parts by weight: 65-70 parts of carrier, 15-20 parts of active agent, 10-15 parts of auxiliary agent and 2-3 parts of modifier, wherein the sum of the components is 100 parts. The invention also discloses a preparation method of the carbonyl sulfide removal catalyst for the blast furnace top gas. The invention relates to a carbonyl sulfide removal catalyst for blast furnace top gas and a preparation method thereof, which utilizes the existing solid waste raw material of a blast furnace and uses CaO and Al with rich content in furnace slag 2 0 3 And SiO 2 As a hydrolysis catalyst carrier, the catalyst has the advantages of greatly reducing the cost of the catalyst and solving the problems of high price, short service life, higher hydrolysis temperature and easy side reaction of the catalyst in the prior art.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a carbonyl sulfide removal catalyst for blast furnace top gas and a preparation method thereof.
Background
The energy consumption of the steel industry in China accounts for 23% of the total industrial energy consumption, 16% of the total national energy consumption, and the pollutant emission accounts for 17% of the total national emission, and the method is a key industry for promoting energy conservation and emission reduction in China.
In 2019, five committees such as the department of ecological environment, the department of improvement and development, the department of industry and correspondence, and the like jointly issue comments about promoting implementation of ultra-low emission in the steel industry, and provide requirements for ultra-low emission indexes in the steel industry. Specifically, the average values of the emission concentrations of the sintering machine head, pellet roasting flue gas particles, sulfur dioxide and nitrogen oxides are respectively not higher than 10 mg/cubic meter, 35 mg/cubic meter and 50 mg/cubic meter when the hours are average; the hourly mean values of the emission concentrations of other main pollution source particles, sulfur dioxide and nitrogen oxides are respectively not higher than 10 mg/cubic meter, 50 mg/cubic meter and 200 mg/cubic meter in principle, and the hourly mean emission concentrations of at least 95% of the time periods per month of the iron and steel enterprises achieving ultralow emission meet the indexes.
The blast furnace plays an important role in a long-flow steel production process, blast furnace gas with the byproduct of 1600-2000 cubic meters is produced per ton of molten iron, the calorific value is 700-800 kcal/cubic meter, and the gas contains carbon monoxide, carbon dioxide, nitrogen, hydrogen and other components and is accompanied by pollutants such as dust, sulfur and the like.
The sulfur in blast furnace gas can be divided into organic sulfur and inorganic sulfur 2 main types. The organic sulfur comprises the following main components: carbonyl sulfide (COS) and carbon disulfide (CS) 2 ) Methyl mercaptan (CH) 4 S), ethanethiol (C) 2 H 6 S), thiophene (C) 4 H 4 S), and the like; the inorganic sulfur comprises the following main components: hydrogen sulfide (H) 2 S), sulfur dioxide (SO) 2 ) And the like. Other organic sulfur is much lower for COS, such as CS 2 The content of the sulfur is about 2 to 3 orders of magnitude lower than COS, the blast furnace gas is a reducing atmosphere, and the inorganic sulfur SO 2 The content is extremely small. Organic sulfur mainly containing carbonyl sulfide (COS) accounts for about 80 percent of the blast furnace gas; with hydrogen sulfide (H) 2 S) mainly comprises inorganic sulfur accounting for about 20 percent.
COS in blast furnace gas is generated in the following mode and reacts with H 2 S Co-existence (reaction formula 1)
C (S-containing) CnHm (S-containing) + O 2 (and/or H) 2 O)→H 2 S+CO 2 →COS+H 2 O (1)
The emission concentration of sulfur dioxide after blast furnace gas is utilized by the working procedures of hot blast furnace, sintering, heating furnace, power generation and the like is 100 mg/cubic meter to 200 mg/cubic meter, and SO in flue gas emitted by some production plants 2 The content of the organic silicon compound is even more than 250 mg/cubic meter, which is far higher than 35 mg/cubic meter and 50 mg/cubic meter required by ultra-low emission indexes, and the organic silicon compound poses serious threats to the environment and the health of people.
In order to solve these problems, many efforts have been made by researchers in the industry, focusing their attention on how to perform an efficient desulfurization process. The traditional acid-base neutralization desulfurization process cannot be efficiently removed, and the environmental protection investment of high-gas users such as subsequent hot blast stoves, sintering machines, pellet furnaces, heating furnaces, boiler power generation and the like can be increased.
Is relatively matureThe method is to arrange a wet washing device behind the TRT device for removing the acid gas, is also called front-end desulfurization, and can effectively remove the acid gas H in the blast furnace gas 2 S、SO 2 、SO 3 The acidic gas can not remove COS in the blast furnace gas, so the COS in the blast furnace gas needs to be firstly converted into H by the hydrolysis of a catalyst 2 S (reaction formula 2), and then conventional wet oxidation desulfurization is adopted for H 2 And S is removed.
The hydrolysis reaction formula is as follows: COS + H 2 O＝H 2 S+CO 2 +35.53kJ/mol (2)
Because the gas yield and the gas pressure fluctuation are large in the production process of the iron-making blast furnace, for example, one blast furnace is 4000m 3 The normal top gas generation amount of the blast furnace is 650000m 3 The gas quantity to be treated is up to 1560 ten thousand cubic meters in one day, the hourly flow of the water gas and the volume ratio of the catalyst in the hydrolysis reactor have certain proportion requirements when the dedusted gas is hydrolyzed and converted, for example, the space velocity is 870/hour in the Japanese Mitsubishi gas desulfurization scheme, if the space velocity is 4000m 3 The volume of the catalyst required for calculating the hourly generation amount of the normal top gas of the blast furnace is about 747m 3 . Therefore, removal of the carbonyl sulfide hydrolysis of blast furnace gas requires a large amount of catalyst. Meanwhile, blast furnace iron making has 24-hour continuity, blast furnace top gas is continuously generated, and the hydrolysis catalyst has to have a long service life so as to meet the conditions of industrial application.
Blast furnace slag is solid waste formed by gangue in ore, ash in fuel and non-volatile components in solvent (generally limestone) in the blast furnace ironmaking process, and 0.25-1.0 ton of slag is discharged per ton of iron according to the ore grade. The main components are CaO, mgO and Al 2 O 3 、SiO 2 And oxides (see table 1).
TABLE 1 main chemical composition of blast furnace slag No. 7 of certain ironworks
US4455466 deals with a method for determining the presence of gamma-Al 2 O 3 The COS hydrolysis catalyst loaded with platinum sulfide has high preparation cost and short service life.
Chinese patent CN1069673 discloses a normal-temperature organic sulfur hydrolysis catalyst in gamma-Al 2 O 3 Loaded with 2-25% of K 2 CO 3 The content of COS is 1-5 mg/m 3 The carbonyl sulfide conversion rate is higher than 95%, but the conversion activity of the raw material gas with high COS is low, although a catalyst loaded with rare earth metal oxide or composite metal oxide is used, a certain catalytic effect can be achieved, but the catalytic conversion of the carbonyl sulfide by the catalyst is difficult to realize in a reducing atmosphere.
The above catalysts have several disadvantages: the hydrolysis temperature is high, and the sulfate poisoning phenomenon is easy to occur; large energy consumption, large investment, high operation cost and easy side reaction. Therefore, the existing solid waste raw materials of the blast furnace are utilized to develop the cheap and long-life catalyst for removing carbonyl sulfide of the blast furnace gas, and the catalyst has great significance for realizing the standard discharge of the blast furnace gas and reducing the post-desulfurization investment and the operation cost of a blast furnace gas user.
Disclosure of Invention
The invention aims to provide a carbonyl sulfide removal catalyst for blast furnace top gas and a preparation method thereof, aiming at the defects of the technology 2 0 3 And SiO 2 As a hydrolysis catalyst carrier, the catalyst has the advantages of greatly reducing the cost of the catalyst and solving the problems of high price, short service life, higher hydrolysis temperature and easy side reaction of the catalyst in the prior art.
In order to realize the purpose, the carbonyl sulfide removal catalyst for the blast furnace top gas is prepared from the following raw materials in parts by weight: 65-70 parts of carrier, 15-20 parts of active agent, 10-15 parts of auxiliary agent and 2-3 parts of modifier, wherein the sum of the components is 100 parts.
Preferably, the carrier is blast furnace slag.
Preferably, the active agent is iron oxide.
Preferably, the auxiliary agent is one or more of zinc oxide, cobalt oxide and copper oxide.
Preferably, the modifier is lanthanum oxide or nanoscale ternary metal oxide, which refers to Ce (15 wt.% La) (5 wt.% Ni) O x 。
Preferably, the blast furnace slag is water-quenched slag, wherein the content of alumina is 13-20 wt.%, and the content of silica is 28-35 wt.%, and the contents of the above components are limited because alumina and silica are good catalyst carriers and can play a skeleton role and increase the mechanical strength and the thermal stability of the catalyst, and the slag in the above component range is a conventional blast furnace smelting product and can ensure the skeleton role of the catalyst.
Preferably, the blast furnace slag is ground into a fine powder, increasing the surface area improves the carrier activity.
A preparation method of the carbonyl sulfide removal catalyst for blast furnace top gas comprises the following steps:
a) Determining 65-70 parts of the carrier by weight, grinding the carrier into fine powder, pouring the fine powder into deionized water with the same volume, stirring and washing, performing solid-liquid separation by a centrifuge, and drying the separated fine powder in a constant-temperature forced air drying box at 105-150 ℃ for 1.5-3.0 h;
b) The required active agent weight portion is 15-20 parts, the auxiliary agent weight portion is 10-15 parts, the modifying agent weight portion is 2-3 parts, and the carrier weight portion is 100 parts in total, the required weight of the corresponding nitrate is calculated according to the proportion of the metal oxide in the active agent, the auxiliary agent and the modifying agent, the nitrate is mixed, and then deionized water is added, so that the volume ratio of the total mass of the nitrate of the active agent, the auxiliary agent and the modifying agent to the ionized water is as follows: 0.95-1 g:1ml, and stirring by magnetic force for 30-45 min to completely dissolve to form a mixed solution;
c) Pouring the fine powder separated in the step A) into the mixed liquid in the step B), uniformly stirring, carrying out ultrasonic treatment in an ultrasonic oscillator for 2-3 h, standing at normal temperature for 12-18 h, and drying in a constant-temperature air-blast drying oven at 105-150 ℃ for 16-18 h to obtain a mixture;
d) Will carry out the stepsIn step C) the mixture is in N 2 Calcining for 4-5 h at 580-620 ℃ in the atmosphere to decompose the metal nitrate precursor, and then cooling to room temperature to obtain a take-out;
e) And D), tabletting the extract obtained in the step D), and crushing and sieving the tablet to 50-100 meshes to obtain a catalyst sample.
Compared with the prior art, the invention has the following advantages:
1. the carrier of the catalyst is blast furnace slag, the activator is oxide of transition metal iron, the sum of the two is 80-90 wt.% of the weight of the catalyst, the cost is low, and conditions are provided for the wide application of the catalyst in the steel industry;
2. the blast furnace slag is a solid waste product of blast furnace ironmaking, and the blast furnace slag is used as a carrier, so that the cost is low, and the environmental resource is protected;
3. the addition of the auxiliary agents of zinc oxide, cobalt oxide and copper oxide improves the removal efficiency of carbonyl sulfide in blast furnace gas, improves the sulfur poisoning resistance of the catalyst and prolongs the service life of the catalyst;
4. when the blast furnace is normally produced, the temperature range of the top gas is 80-270 ℃, and the hydrolysis conversion rate of the modified catalyst is over 90 percent at the temperature of 60-300 ℃, so that the application of the catalyst for desulfurization does not need to adjust the temperature of the gas, greatly saves energy consumption and reduces the desulfurization cost.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example one
A) Weighing 65g of No. 8 blast furnace slag, wherein the chemical components are shown in Table 2, grinding the blast furnace slag into fine powder, pouring the fine powder into 81ml of deionized water, stirring and washing the fine powder, performing solid-liquid separation by using a centrifugal machine, and drying the separated fine powder in a constant-temperature blast drying oven at 105 ℃ for 2 hours;
TABLE 2 blast furnace slag No. 8 of certain ironworks main chemical composition (2020.8.10)
B) In the embodiment, 20g of active agent iron oxide, 13g of auxiliary agent cobalt oxide and 2g of modifier lanthanum oxide are required, the required amounts of corresponding nitrates, namely 60.5g of iron nitrate, 31.7g of cobalt nitrate and 4g of lanthanum nitrate are weighed according to the metal oxide proportion, mixed, then 96ml of deionized water is added, and the mixture is magnetically stirred for 30min and completely dissolved to form a mixed solution;
c) Pouring the fine powder separated in the step A) into the mixed solution, uniformly stirring, carrying out ultrasonic treatment in an ultrasonic oscillator for 2 hours, standing for 12 hours at normal temperature, and drying in a constant-temperature air-blast drying oven at 105 ℃ for 16 hours to obtain a mixture;
d) Mixing the mixture in N 2 Calcining for 4h at 580 ℃ in the atmosphere to decompose the metal nitrate precursor, and then cooling to room temperature to obtain a taken-out object;
e) Taking out the materials, crushing and sieving the materials into 80 meshes after tabletting to obtain a catalyst sample.
The catalyst sample is loaded into a fixed bed quartz reactor with d =14mm, a built-in porous sieve plate is used for placing catalyst particles with 50-100 meshes, and the reaction space velocity is controlled to be 5000h -1 The pressure is 0.1Mpa, the reaction temperature is 200 ℃, the gas is blast furnace gas, wherein the organic sulfur is carbonyl sulfur 150mg/m 3 The flow rate was adjusted to 1L/min, the time was 24 hours, the carbonyl sulfide concentration before and after the reaction was detected and analyzed by a gas chromatograph GC-7820 equipped with TCD and FPD detectors 1 time at 2 hours intervals, and the results are shown in Table 3.
Table 3 example-24 h conversion efficiency of blast furnace gas carbonyl sulfide
The results show that the hydrolysis conversion rate of the carbonyl sulfide of the blast furnace gas reaches over 90 percent within 24 hours at the temperature of 200 ℃, the activity of the catalyst is not obviously attenuated within 24 hours, and the catalyst has stronger sulfur poisoning resistance and longer service life.
Example two
A) Weighing 70g of No. 7 blast furnace slag, wherein the chemical components of the blast furnace slag are shown in Table 4, grinding the blast furnace slag into fine powder, pouring the fine powder into 87ml of deionized water, stirring and washing the fine powder, performing solid-liquid separation by using a centrifugal machine, and drying the separated fine powder in a constant-temperature blast drying oven at the temperature of 130 ℃ for 2 hours;
TABLE 4 blast furnace slag No. 7 of certain ironworks main chemical composition (2020.9.12)
B) In this example, 18g of iron oxide as an activator, 9g of zinc oxide as an auxiliary agent, and 3g of ternary metal oxide as a modifier were required, and the required amounts of corresponding nitrates, i.e., 54.5g of iron nitrate, 21g of zinc nitrate, and Ce (15 wt.% La) (5 wt.% Ni) (NO), were weighed based on the above metal oxide ratios 3 ) x 4.7g, mixing, then adding 80ml of deionized water, and magnetically stirring for 40min to completely dissolve to form a mixed solution;
c) Pouring the fine powder separated in the step A) into the mixed solution, uniformly stirring, carrying out ultrasonic treatment in an ultrasonic oscillator for 2.5 hours, standing for 15 hours at normal temperature, and drying in a constant-temperature air-blast drying oven at 130 ℃ for 17 hours to obtain a mixture;
d) Mixing the mixture in N 2 Calcining for 4.5h at 600 ℃ in the atmosphere to decompose the metal nitrate precursor, and then cooling to room temperature to obtain a taken-out material;
e) Taking out the materials, crushing and sieving the materials into 50 meshes after tabletting to obtain a catalyst sample.
The catalyst sample is loaded into a fixed bed quartz reactor with d =14mm, a built-in porous sieve plate is used for placing 50-100 meshes of catalyst particles, and the reaction space velocity is controlled to be 5000h -1 The pressure is 0.1Mpa, the reaction temperature is 140 ℃, the gas is blast furnace gas, wherein the organic sulfur is carbonyl sulfide 190mg/m3, the flow is adjusted to be 1L/min, the investigation time is 24h, the carbonyl sulfide concentration before and after the reaction is detected and analyzed by a gas chromatograph GC-7820 provided with TCD and FPD detectors, the analysis is carried out for 1 time at intervals of 2h, and the results are shown in Table 5.
TABLE 5 example 24h conversion efficiency of carbonyl sulfide of blast furnace gas
The results show that the hydrolysis conversion rate of the carbonyl sulfide of the blast furnace gas reaches over 90 percent within 24 hours at the temperature of 140 ℃, the activity of the catalyst is not obviously attenuated within 24 hours, and the catalyst has stronger sulfur poisoning resistance and longer service life.
EXAMPLE III
A) Weighing 68g of blast furnace slag No. 6, wherein the chemical components are shown in Table 6, grinding the blast furnace slag No. 6 into fine powder, pouring the fine powder into 85ml of deionized water, stirring and washing the fine powder, performing solid-liquid separation by using a centrifugal machine, and drying the separated fine powder in a constant-temperature blast drying oven at 150 ℃ for 3 hours;
TABLE 6 blast furnace slag No. 6 of iron works as main chemical composition (2021.4.13)
B) In this example, 16g of iron oxide as an activator, 13g of copper oxide as an auxiliary agent, and 3g of ternary metal oxide as a modifier were required, and the required amounts of corresponding nitrates, i.e., 48.4g of iron nitrate, 30.7g of copper nitrate, and Ce (15 wt.% La) (5 wt.% Ni) (NO), were weighed based on the above metal oxide ratios 3 ) x 4.7g, mixing, adding 81ml of deionized water, and magnetically stirring for 45min to completely dissolve to form a mixed solution;
c) Pouring the fine powder separated in the step A) into the mixed solution, uniformly stirring, performing ultrasonic treatment in an ultrasonic oscillator for 3 hours, standing at normal temperature for 18 hours, and drying in a constant-temperature air-blast drying oven at 150 ℃ for 18 hours to obtain a mixture;
d) Mixing the mixture in N 2 Calcining for 5h at 620 ℃ in the atmosphere to decompose the metal nitrate precursor, and then cooling to room temperature to obtain a taken-out object;
e) Taking out the materials, crushing and sieving the materials into 100 meshes after tabletting to obtain a catalyst sample.
The catalyst sample is loaded into a fixed bed quartz reactor with d =14mm, a built-in porous sieve plate is used for placing catalyst particles with 50-100 meshes, and the reaction space velocity is controlled to be 5000h -1 The pressure is 0.1Mpa, the reaction temperature is 170 ℃, the gas is blast furnace gas, wherein the organic sulfur is carbonyl sulfur of 164mg/m 3 The flow rate was adjusted to 1L/min, the time was 24 hours, and the carbonyl sulfide concentration before and after the reaction was detected and analyzed by a gas chromatograph GC-7820 equipped with a TCD and FPD detector 1 time at 2 hours intervals, and the results are shown in Table 7.
TABLE 7 example 24h conversion efficiency of cos in blast furnace gas
The results show that the hydrolysis conversion rate of the carbonyl sulfide of the blast furnace gas reaches over 90 percent within 24 hours at the temperature of 170 ℃, the activity of the catalyst is not obviously attenuated within 24 hours, and the catalyst has stronger sulfur poisoning resistance and longer service life.
The invention relates to a carbonyl sulfide removal catalyst for blast furnace top gas and a preparation method thereof, wherein a carrier of the catalyst is blast furnace slag, an activator is oxide of transition metal iron, the sum of the two is 80-90 wt.% of the weight of the catalyst, the cost is low, and conditions are provided for the wide application of the catalyst in the steel industry; the blast furnace slag is a solid waste product of blast furnace ironmaking, and the blast furnace slag is used as a carrier, so that the cost is low, and the environmental resource is protected; the addition of the auxiliary agents of zinc oxide, cobalt oxide and copper oxide improves the removal efficiency of carbonyl sulfide in blast furnace gas, improves the sulfur poisoning resistance of the catalyst and prolongs the service life of the catalyst; when the blast furnace is normally produced, the temperature range of the top gas is 80-270 ℃, and the hydrolysis conversion rate of the modified catalyst is over 90 percent at the temperature of 60-300 ℃, so that the application of the catalyst for desulfurization does not need to adjust the temperature of the gas, greatly saves energy consumption and reduces the desulfurization cost.
Claims (2)
1. The carbonyl sulfide removing catalyst for blast furnace top gas features that: the material is prepared from the following raw materials in parts by weight: 65-70 parts of a carrier, 15-20 parts of an active agent, 10-15 parts of an auxiliary agent and 2-3 parts of a modifying agent, wherein the sum of the components is 100 parts, the carrier is blast furnace slag, the active agent is ferric oxide, the blast furnace slag is water-quenched slag, the content of aluminum oxide is 13-20 wt%, the content of silicon oxide is 28-35 wt%, the auxiliary agent is one or more of zinc oxide, cobalt oxide and copper oxide, the modifying agent is lanthanum oxide or a nanoscale ternary metal oxide, and the ternary metal oxide is Ce (15 wt.% La) (5 wt.% Ni) O (O) O (5 wt.% Ni) x The blast furnace slag is ground into a fine powder.
2. A method for preparing the catalyst for removing carbonyl sulfide from blast furnace top gas as defined in claim 1, wherein the method comprises the following steps: the method comprises the following steps:
a) Determining 65-70 parts by weight of the carrier, grinding the carrier into fine powder, pouring the fine powder into deionized water with the same volume, stirring and washing, performing solid-liquid separation by a centrifuge, and drying the separated fine powder in a constant-temperature air-blast drying oven at 105-150 ℃ for 1.5-3.0 h;
b) Taking 15-20 parts by weight of an active agent, 10-15 parts by weight of an auxiliary agent, 2-3 parts by weight of a modifier and 100 parts by weight of a carrier, calculating the required weight of corresponding nitrate according to the proportion of metal oxides in the active agent, the auxiliary agent and the modifier, mixing, and then adding deionized water to ensure that the volume ratio of the total mass of the nitrate of the active agent, the auxiliary agent and the modifier to the volume of the deionized water is as follows: 0.95-1 g:1ml, and stirring by magnetic force for 30-45 min to completely dissolve to form a mixed solution;
c) Pouring the fine powder separated in the step A) into the mixed solution in the step B), uniformly stirring, performing ultrasonic treatment in an ultrasonic oscillator for 2-3 h, standing at normal temperature for 12-18 h, and drying in a constant-temperature forced air drying oven at 105-150 ℃ for 16-18 h to obtain a mixture;
d) Mixing the mixture obtained in the step C) in N 2 Calcining for 4-5 h at 580-620 ℃ in the atmosphere to decompose the metal nitrate precursor, and then cooling to room temperature to obtain a take-out;
e) And D), tabletting the extract obtained in the step D), and crushing and sieving the tablet to 50-100 meshes to obtain a catalyst sample.
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